Slushing oil compositions



I Patented Aug. 14, i945 SLUSHING OIL COMPOSITIONS Gordon W. Duncan, Scotch Plains, N. 1., asslgnor to Standard Oil Development Company, acor- 4 poration of Delaware No Drawing. Application January 2, 1941, Serial No. 372,831

1 Claim. (01. 106-14) This invention relates to slushing compositions, that is, to non-drying compositions of matter for arrestin preventing and inhibiting the corrosion of metals.

The corrosion of a metal is considered the result of chemical reactions between the environ ment and the metallic surface due to differences in electromotive forces in and about the surface of the metal. By coating metallic surfaces with an inert, impervious film, the development of these electrochemical relations can be impeded and ar-- rested and thus active corrosion prevented. The use of a slushing composition involves the formation of a relatively thick, viscous liquid or semisolid layer which is easily removable from the surfaces over which it is spread by wiping with a cloth or flushing with a readily available solvent. More durable coatings may be obtained by employing a more viscous oil base and heating the mixture prior to application to allow better treatment of the surface. In no case, however. is the protective layer of the nature of a difllcultly-removable varnish-like layer. The use of slushing compositions is particularly advantageous when metallic surfaces have to be temporarily protected such as engine parts during storage or tubing during shipment.

It has now been found that when small amounts of salts of certain nitrogen base compounds and organic acids are incorporated in slushing compositions the composite is characterized by marked anti-corrosive properties and the capacity in many cases of the composites to displace moisture from the metallic surfaces. The compositions of the invention are therefore improved slushing oil compositions which contain in addition to the usual constituents of the nature of a protective base material which may be a fatty compound, a mineral oil of about lubricating consistency or a more resistant non-drying coating material, small amounts of salts of nitrogen base compounds such as the organic amines and heterocyclic nitrogen bases, and organic acids. These new type addition agents are either dissolved or finely dispersed in anti-rust compositions. A type of anti-rust composition which is appreciably improved by the addition thereto of the compounds of this invention is that disclosed in Patent 2,182,992. These compositions are composed of a petroleum oil of lubricating oil consistency blended with a fatty compound, such as degras, and mahogany soap such as an alkaline metal soap of the oil-soluble sulfonates derived from petroleum by treating oils with concentrated sulfuric acid. The following formula is a specific example:

. 'Per cent Petroleum oil (750 secs. Saybolt at 100 F.) 85 50% oil solution of sodium salts of oil-soluble sulfonic acids formed on treating petroleum stocks with concentrated sulfuric acid l Degras All of the common amines, that is, the readily available primary, secondary and tertiary amines, in combination with fatty or naphthenic acids have been found to be very eflective anti-corrosive agents when incorporated in hydrocarbon and fatty base protective compositions. A preferred class of compounds are the salts of those amines boiling above about 150 F. but which are sufliciently basic to form relatively stable soaps with the respective acids. Where water displacement properties are of importance, it has been found desirable to employ those soaps which have atflnity for water or appreciable solubility in water.

Amines which uponreaction with an organic acid are hydrophilic are the alkylol amines such as phenyl ethanolamine, diethyl ethanolamine or ethyl diethanolamine, the lower molecular weight aliphatic primary amines such as the amyl and hexyl amines and the lower molecular weight 30 heterocyclic nitrogen bases such as pyridine, quinoline and morpholine. The acids which are suitable for reaction with these amines to prepare hydrophilic soaps are the unsaturated fatty acids of between and carbon atoms which react with the particular amine to form a stable compound. Besides this group of unsaturated fatty acids,the naphthenic acids derived from petroleum especially those from the naphtha, gas oil and lubricating oil ranges, are advantageous in this regard. For the preparation of soaps within the scope of this invention however, that is for incorporation in compositions upon which no particular emphasis is laid as to their water displacing ability, any amine which reacts with an organic acid to form a stable compound may be employed. The saturated fatty acids above carbon atoms are the least desirable 'acid constituents of the soaps suitable for compositions according to the. present invention. I

The amine salts employed in this invention as additives in the various compositions may be pre pared by the reaction of the amine or mixture of amines with an organic acid or mixture of such acids. Natural fats may be used as a source of the fatty acids and when so employed the fats may be saponifled by heating with the amine at a high temperature and thus the amine salt is prepared directly. The naphthenate salts may be formed-from the naphthenic acids derived from any of the naphthenic acid containing mineral oil crudes or fractions thereof. The acids may be extracted from the petroleum distillates by any of the known processes such as by distilling over caustic soda, extracting the sodium naphthenates invention, particularly the amine soaps in amounts between 0.25% and 5.0%. and preferably between 1 and 3% by weight to mineral or vegetable oil or wax bases. In the case of vegetable oils, such as castor oil, amine soaps in amounts between 1 and 5%, with or without a diluent such as alcohol, are effective rust preventative compositions. Furthermore, these compositions have substantially no eifect upon rubber.

The efilcacy of coating compositions is evaluated by certain standard tests of which the humidifier test and displacement of various aqueous solutions are the more important.

HUMDDIFIER TEST Tssr Psoczmms Sand blasted panels of hot rolled steel (automobile body sheet steel) are dipped into slushing compound samples, then maintained vertically in a box for 16 hours under ordinary room conditions. Compounds containing petrolatum are applied at temperatures above their melting point and fluid products are applied at room temperatures. The coated panels are thenplaced and spaced apart in an upright position in a humidifier chamber having a. volume of 16 cu. ft. and air of a given humidity and temperature is injected at a rate 01-12 cu. ft./hr. In the test the temperature is maintained at 100 F., the humidity at The time, in hours. for a panel subjected under these conditions to develop a rusting appearance is observed and recorded as the resistance life of the coating composition.

The following data illustrate the rust preventative effectiveness of various compositions:

Humidifier test [100' ilk-100% humidity] Hours to Compound initial rusts 1 Coastal SAE 40 lubricating oil 2 0 Coastal 2% diethylethsnolsmine oleste. c) Coastal 2% dicyclohexylamine naphthenste. 192 2 slammg coasts] BAE 40 lubricating oil 30% petro- 24 b) 70% Coastsl SAE 40 lubricating 011 dicyclohexylsmine nsphthenste 250+ (a) Petrolstum 24-48 (h) Petrolstum+ 1% dicyclohexylsmine nsphthensm 200+ so Peimlstum 1% morpholine nsphthenste...-. 230+ e Clstoro 3 (b Castor oil 5% morpholine oleste no WATER DIBPIACEIIEN'I' TEST Sand blasted panels ot'hot rolled steel s dipped in an aqueous solution and while still wet are immediately immersed in the slushing compounds for a period of one minute. The

in the laboratory atmosphere, then washed with naphtha, and examined for signs of corrosion. In a series of tests, the effects of many different amine soaps in a mixture of petroleum naphtha and 25% SAE 20 mineral lubricating oil were investigated with the following results:

Tap water displacement tests V corrosion 1. 7 naphtha+25% SAE20 lubricat-' ingoil (A) Severe 2. A+2% morpholine naphthenaie-- None 1 3. A+2% morpholine oleate None 4. A+2% morpholine soap of oxidized wax acids, (partially solublelL--- Light 5. A+2% diethylethanolamine naphthenate None 6. A+2% diethylethanolamine oleate- None 7. A+2% diethylethanolamine soap oi oxidized wax acids (partially soluble) Light 8. A+2'% dicyclohexylamine naphthenate Trace 9. A+2% dicyclohexylamine soap of oxidized wax acids Light 10. A+2% dicyclohexylamine oleate Medium -()xidized wax acids include both unsaturated and saturated iatty acids.

In another test similarly conducted the ability or these agents to displace corrosive solutions other than tap water is evaluated.

Corrosion by aqueous solution displacanent-test 0.7% sodium chloride, 0.4% 1mm scid, 0.1% urea in distilled water.

The addition agents of this invention are effective as corrosion inhibitors and agents ior displacing moisture from metallic surfaces when incorporated in protective base compositions. The resultant compositions are eii'ective for protecting finely-polished surfaces and for heavy machinery parts exposed to weathering. Individual compontions have characteristics adapted for the particular uses for which theyare to be employed. The

consistency of thevarious tions is determinedbytheservicereqmrementsandthemannor in which the compositions are to be an tothesuriacestobeprotected. Thus.inthe oi' the protection of highly finished mete-l suchsscutlemandthennelysmundenghie surfaces the compomtions may contain in addition to the protective base a volatile material such as. gasoline which some time stter'applicstion ottbej composition to the surfaces ev porates and leaves behindalayerofprotectivemsterisloftheboss' and addition agent of this invention. In other cases it is preferable to employ as anti-rust compositions materials or which are semi-solid or evensolidinordertowithstsndths ponelssrethensuspendedverticsllyior2hours ll eli'ectsotexposm e'toheavyrainssndothersting compositions of suitable consistency and protective quality no deterioration'of the aniline surfaces and therefore of engine eiilciency occurs as the result of storage or delays in shipment through varied atmospheric and climatic condi-' tions. Furthermore, compositiom of this invention that are suitable for use in the protection of engine assemblies have suitable solubilities in light lubricating oils which are generally employed as solvents to flush the system before placing the.

engine in service. An added p perty of such compositions is that the constituents which are incorporated have no harmful effect upon lubricating oils which are subsequently employed in the lubrication of the engine. The addition agents of this invention as a group do not exert any deleterious effect upon mineral lubricating oils and therefore their incorporation-in slushing composivantageous. I

Although the mechanism and operation of the tions m cnaine assemblies is particularly m aminesoaps inthevarlous-compositionsarenot undeifstoodandiliisnotdeairedtobelifitedto any particular theory as to the operation thereof, itisbelievedthattheaminesoapspresentinthe compositions have some etfect in neutralizing nascent .acids formed nearthe surface of the metals.

. It is believed that the scope have an actiondiifer-' ent from thatwhen dissolved in water and have capacity to inhibit the development of electrochemical relations in the surface of the metal.

. It is not intended that this invention be limited to any of the particular examples which have been Y given'for purpose of illustration nor by any of the theories as to the operation of the invention,

but only by the app nded claims in which it is desired to claim all th novelty inherent in the invention.

What is claimed is:

A slushing composition comprising a viscous petroleum fraction to which is added 5% degras,

10% of a 50% oil solution of sodium salts of oilsoluble sulfonic acids formed on treating petroleum stocks with concentrated sulfuric acid and 0.25% to 5% of dicyclohexylamine naphthenate.

I GORDON w. Duncan. 

